EP0255650A2 - Method for the production of indanes - Google Patents
Method for the production of indanes Download PDFInfo
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- EP0255650A2 EP0255650A2 EP87110537A EP87110537A EP0255650A2 EP 0255650 A2 EP0255650 A2 EP 0255650A2 EP 87110537 A EP87110537 A EP 87110537A EP 87110537 A EP87110537 A EP 87110537A EP 0255650 A2 EP0255650 A2 EP 0255650A2
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- olefins
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- titanium tetrachloride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/135—Compounds comprising a halogen and titanum, zirconium, hafnium, germanium, tin or lead
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
Definitions
- the present invention relates to a process for the preparation of indanes by reacting optionally substituted benzyl halides with olefins in the presence of a Lewis acid as a catalyst.
- the invention was therefore based on the object of finding a process by which indane is processed in a technically simple manner by reaction of optionally substituted benzyl with Lewis acid halides with olefins are obtained in high yields and space-time yields and in which olefins which are not substituted by aryl radicals can be used.
- benzyl halides I e.g. optionally substituted benzyl fluorides, chlorides or bromides implemented. Because benzyl chlorides are the most accessible, they are preferred.
- substituted benzyfluorides or bromides is e.g. in J. Org. Chem. 29, 2685-87 (1964).
- the radicals R1 and R2 are, in addition to hydrogen, branched or unbranched alkyl radicals, for example C1- to C12-, in particular C1- to C8-, preferably C1-to C4-alkyl radicals, alkoxy radicals, for example C1- to C8-, preferably C1- to C4- Alkoxy radicals, C5- or C6-cycloalkyl radicals, aryl radicals, for example phenyl radicals bearing phenyl or inert substituents, such as halogen-, alkyl- or alkoxy-substituted phenyl radicals, aryloxy radicals, for example the phenoxy radical, and aralkyl radicals, for example C6 to C12 aralkyl radicals.
- alkyl radicals for example C1- to C12-, in particular C1- to C8-, preferably C1-to C4-alkyl radicals, alkoxy radicals, for example C
- the radical R3 has the meaning given for R1 and R2 and can also be used for halogen, e.g. Fluorine, chlorine or bromine or an ortho-condensed ring system, e.g. together with the phenyl core form a naphthyl system.
- halogen e.g. Fluorine, chlorine or bromine
- an ortho-condensed ring system e.g. together with the phenyl core form a naphthyl system.
- the radicals R4 to R7 represent hydrogen or an alkyl radical which is unbranched in the alpha position, but can otherwise be branched.
- the alkyl residues can e.g. Contain 1 to 12, especially 1 to 8, preferably 1 to 4 carbon atoms, e.g. be the methyl, ethyl, propyl, butyl, 2-methyl-butyl, 3,3-dimethylbutyl, pentyl, hexyl or octyl radical.
- di, tri and tetra substituted olefins can be reacted e.g.
- olefin In general, 1.5 to 4, advantageously 2 to 3, in particular 2 to 2.5, moles of olefin can be used per mole of benzyl halide I. Lower, e.g. Equimolar amounts of olefins are possible, but not expedient, since the hydrogen halide formed in the reaction can possibly be bound by the olefin and thereby consumed. Higher excesses of olefin, on the other hand, are possible, but generally have no advantages.
- the reaction is carried out in the presence of catalytic amounts of titanium tetrachloride, since this catalyst particularly favors the ring closure reaction to indane.
- the amount of catalyst is expediently from 0.002 to 0.2, in particular 0.004 to 0.04, preferably 0.01 to 0.03 mol, based on 1 mol of benzyl halide I. With smaller and higher amounts of catalyst, the formation of by-products generally increases.
- the reaction can be carried out in the presence or absence of a solvent.
- Solvents which can be used are the solvents customary for Friedel-CraftsSHY reactions, such as aromatic or aliphatic hydrocarbons, ethers or halogenated hydrocarbons, e.g. Benzene, toluene, hexane, diethyl ether, dichloromethane, chloroform of solvents are not necessary, which is particularly characteristic of the process according to the invention.
- the reaction temperature depends on the reactivity of the starting materials. It is usually around -20 to + 40 ° C. Lower temperatures are possible, but generally not necessary.
- the procedure can be carried out in a manner known per se at positive pressure, negative pressure or advantageously at atmospheric pressure, discontinuously or continuously using the techniques customary for this.
- the olefin can be introduced at the reaction temperature together with titanium tetrachloride and the benzyl halide I added.
- the reaction mixture obtained is worked up in a conventional manner, e.g. the catalyst is destroyed by adding water, excess olefin and volatile by-products are distilled off and the indane contained in the residue is e.g. purified by distillation or recrystallization or used directly.
- Optionally substituted indanes in particular polyalkyl-substituted indanes, can be obtained in good yields in a technically simple manner by the process according to the invention.
- the products that are intermediates e.g. of interest for the production of fragrances are often so pure that they can be processed directly without purification by distillation.
- the production of bicyclic aromatic musk fragrances such as galaxolide from the indanes obtained according to the invention is e.g. in EP 89207 or U.S. Patents 4,265,818 and 4,315,951.
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Herstellung von Indanen durch Umsetzung von gegebenenfalls substituierten Benzylhalogeniden mit Olefinen in Gegenwart einer Lewis-Säure als Katalysator, indem man Benzylhalogenide I <IMAGE> (mit R¹ und R² = Wasserstoff, Alkyl-, Alkoxy-, Cycloalkyl-, Aryl-, Aryloxy-, Aralkylrest R³ = R¹, Halogen oder ein ortho-kondensiertes Ringsystem X = Halogen) mit Olefinen II <IMAGE> (mit R<4> bis R<7> = Wasserstoff, in alpha-Stellung unverzweigter Alkylrest) in Gegenwart katalytischer Mengen an Titantetrachlorid umsetzt.Preparation of indanes by reacting optionally substituted benzyl halides with olefins in the presence of a Lewis acid as a catalyst by using benzyl halides I <IMAGE> (where R¹ and R² = hydrogen, alkyl, alkoxy, cycloalkyl, aryl, aryloxy, Aralkyl residue R³ = R¹, halogen or an ortho-fused ring system X = halogen) with olefins II <IMAGE> (with R <4> to R <7> = hydrogen, in the alpha-position unbranched alkyl residue) in the presence of catalytic amounts of titanium tetrachloride .
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Indanen durch Umsetzung von gegebenenfalls substituierten Benzylhalogeniden mit Olefinen in Gegenwart einer Lewis-Säure als Katalysator.The present invention relates to a process for the preparation of indanes by reacting optionally substituted benzyl halides with olefins in the presence of a Lewis acid as a catalyst.
Die Umsetzung von substituierten Benzylhalogeniden mit Olefinen wie Propen, Isobuten und 1-Methylstyrol in Gegenwart von Zinkchlorid bzw. Zinkchloridetherat in Dichlormethan als Lösungsmittel wird in J. Org. Chem., Bd. 48, 1159-1165 (1983) beschrieben. Dabei wird sowohl bei tiefen Temperaturen von -78°C als auch bei Temperaturen von 0 bis +80°C in der Regel das 1 : 1-Additionsprodukt erhalten. (s. auch J. Org. Chem. Bd. 29, 2685-2687, 1964). Die nachfolgende Ringschlußreaktion zum Indan wird lediglich bei Umsetzung von 1-Chlor-1-phenylethan mit 1-Methylstyrol bei +50°C und bei Umsetzung von Tritylchlorid mit Isobuten bei 0°C in Ausbeuten von 80 bzw. 21 % beobachtet. Aus der Dissertation von W. Striepe, Erlangen, 1984, Seiten 28, 29 und 119 geht hervor, daß Indane erhalten werden können, wenn man p-Methylcumylchlorid mit alkylsubstituierten Olefinen zunächst bei tiefer Temperatur in Gegenwart von Zinkchloridetherat umsetzt und dann das Reaktionsgemisch innerhalb von 10 h auf Raumtemperatur erwärmen läßt. Dieses Verfahren ist jedoch aufgrund der tiefen Temperatur und einer geringen Raum-Zeit-Ausbeute technisch wenig brauchbar.The reaction of substituted benzyl halides with olefins such as propene, isobutene and 1-methylstyrene in the presence of zinc chloride or zinc chloride etherate in dichloromethane as solvent is described in J. Org. Chem., Vol. 48, 1159-1165 (1983). The 1: 1 addition product is generally obtained both at low temperatures of -78 ° C and at temperatures from 0 to + 80 ° C. (see also J. Org. Chem. Vol. 29, 2685-2687, 1964). The subsequent ring closure reaction to indane is observed only when 1-chloro-1-phenylethane is reacted with 1-methylstyrene at + 50 ° C and when trityl chloride is reacted with isobutene at 0 ° C in yields of 80 or 21%. From the dissertation by W. Striepe, Erlangen, 1984, pages 28, 29 and 119, it can be seen that indanes can be obtained if p-methylcumyl chloride is reacted with alkyl-substituted olefins first at low temperature in the presence of zinc chloride etherate and then the reaction mixture within Allow to warm to room temperature for 10 h. However, due to the low temperature and a low space-time yield, this method is technically of little use.
Aus J. Org. Chem., Bd. 44, 3022-3028 (1979), und J. Chem. Res. (S) 1979, S. 184 u. 185 ist bekannt, daß die Umsetzung von Phenyl- und Diphenylalkylchloriden mit phenylsubsituierten Alkenen wie Phenylpropen und Stilben in Gegenwart von Zinkchlorid in Dichlormethan als Lösungsmittel und bei Temperaturen von 20 bis 40°C in Ausbeuten von 70 bis 84 % zu den entsprechenden Indanen führen. Dagegen fällt mit Styrol als Olefin das 1 : 1-Additionsprodukt als Hauptprodukt an.From J. Org. Chem., Vol. 44, 3022-3028 (1979), and J. Chem. Res. (S) 1979, pp. 184 u. 185 is known that the reaction of phenyl and diphenylalkyl chlorides with phenyl-substituted alkenes such as phenylpropene and stilbene in the presence of zinc chloride in dichloromethane as solvent and at temperatures of 20 to 40 ° C in yields of 70 to 84% lead to the corresponding indanes. In contrast, with styrene as the olefin, the 1: 1 addition product is obtained as the main product.
Nachteilig an den beschriebenen Verfahren ist die zum Teil geringe bis mäßige Ausbeute an Indanen, die geringe Anwendungsbreite hinsichtlich der Ausgangskomponenten bei für technische Prozesse interessanten Temperaturbereichen, sowie die Notwendigkeit, die Umsetzung in Gegenwart von Lösungsmitteln, insbesondere von toxikologisch nicht unbedenklichen halogenierten Kohlenwasserstoffen durchzuführen.Disadvantages of the processes described are the sometimes low to moderate yield of indanes, the narrow range of uses with regard to the starting components in temperature ranges which are of interest for technical processes, and the need to carry out the reaction in the presence of solvents, in particular of halogenated hydrocarbons which are not toxicologically acceptable.
Der Erfindung lag daher die Aufgabe zugrunde, ein Verfahren zu finden, nach dem Indane auf technisch einfache Weise durch Lewissäure-katalysierte Umsetzung von gegebenenfalls substituierten Benzyl halogeniden mit Olefinen in hohen Ausbeuten und Raum-Zeit-Ausbeuten anfallen und bei dem Olefine eingesetzt werden können, die nicht durch Arylreste substituiert sind.The invention was therefore based on the object of finding a process by which indane is processed in a technically simple manner by reaction of optionally substituted benzyl with Lewis acid halides with olefins are obtained in high yields and space-time yields and in which olefins which are not substituted by aryl radicals can be used.
Demgemäß wurde ein Verfahren zur Herstellung von Indanen durch Umsetzung von gegebenenfalls substituierten Benzylhalogeniden mit Olefinen in Gegenwart einer Lewis-Säure als Katalysator gefunden, das dadurch gekennzeichnet ist, daß man Benzylhalogenide der Formel I
Nach dem erfindungsgemäßen Verfahren werden Benzylhalogenide I, z.B. ggf. substituierte Benzylfluoride, -chloride oder -bromide umgesetzt. Da Benzylchloride am einfachsten zugänglich sind, werden sie bevorzugt verwendet. Die Herstellung von substituierten Benzyyfluoriden oder -bromiden ist z.B. in J. Org. Chem. 29, 2685-87 (1964) beschrieben.In the process according to the invention, benzyl halides I, e.g. optionally substituted benzyl fluorides, chlorides or bromides implemented. Because benzyl chlorides are the most accessible, they are preferred. The production of substituted benzyfluorides or bromides is e.g. in J. Org. Chem. 29, 2685-87 (1964).
Als Reste R¹ und R² kommen neben Wasserstoff verzweigte oder unverzweigte Alkylreste, z.B. C₁- bis C₁₂-, insbesondere C₁- bis C₈-, vorzugsweise C₁-bis C₄-Alkylreste, Alkoxyreste, z.B. C₁- bis C₈-, vorzugsweise C₁- bis C₄-Alkoxyreste, C₅- oder C₆-Cycloalkylreste, Arylreste, z.B. Phenyl- oder inerte Substituenten tragende Phenylreste wie halogen-, alkyl- oder alkoxysubstituierte Phenylreste, Aryloxyreste z.B. der Phenoxyrest sowie Aralkylreste, z.B. C₆- bis C₁₂-Aralkylreste in Betracht. Beispielsweise seien der Methyl-, Ethyl-, Propyl-, Isopropyl-, Butyl-, tert.-Butyl-, Pentyl-, Hexyl-, Octyl-, Methoxy-, Ethoxy-, Cyclopentyl-, Cyclohexyl-, Phenyl-, p-Chlor-phenyl-, Tolyl-, Phenoxy-, Phenylethyl- oder Benzylrest aufgeführt.The radicals R¹ and R² are, in addition to hydrogen, branched or unbranched alkyl radicals, for example C₁- to C₁₂-, in particular C₁- to C₈-, preferably C₁-to C₄-alkyl radicals, alkoxy radicals, for example C₁- to C₈-, preferably C₁- to C₄- Alkoxy radicals, C₅- or C₆-cycloalkyl radicals, aryl radicals, for example phenyl radicals bearing phenyl or inert substituents, such as halogen-, alkyl- or alkoxy-substituted phenyl radicals, aryloxy radicals, for example the phenoxy radical, and aralkyl radicals, for example C₆ to C₁₂ aralkyl radicals. For example, the methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, octyl, methoxy, ethoxy, cyclopentyl, cyclohexyl, phenyl, p- Chlorophenyl, tolyl, phenoxy, phenylethyl or benzyl radical listed.
Der Rest R³ hat die für R¹ und R² genannte Bedeutung und kann darüber hinaus für Halogen, z.B. Fluor, Chlor oder Brom stehen oder ein ortho-kondensiertes Ringsystem, z.B. zusammem mit dem Phenylkern ein Naphthylsystem, bilden.The radical R³ has the meaning given for R¹ and R² and can also be used for halogen, e.g. Fluorine, chlorine or bromine or an ortho-condensed ring system, e.g. together with the phenyl core form a naphthyl system.
In den Olefinen II stehen die Reste R⁴ bis R⁷ für Wasserstoff oder einen Alkylrest, der in alpha-Stellung unverzweigt ist, ansonsten aber verzweigt sein kann. Die Alkylreste können z.B. 1 bis 12, insbesondere 1 bis 8, vorzugsweise 1 bis 4 Kohlenstoffatome enthalten, z.B. sei der Methyl-, Ethyl-, Propyl-, Butyl-, 2-Methyl-butyl-, 3,3-Dimethylbutyl-, Pentyl-, Hexyl- oder Octylrest aufgeführt. Vorzugsweise können di-, tri-und tetra-substituierte Olefine umgesetzt werden, z.B. Propen, But-1-en, Isobuten, Pent-1-en, Hex-1-en, But-2-en, 2-Methylbut-2-en, 3-Methylpent-2-en, 3,5-Dimetnylhex-2-en, Tetramethylethylen.In the olefins II, the radicals R⁴ to R⁷ represent hydrogen or an alkyl radical which is unbranched in the alpha position, but can otherwise be branched. The alkyl residues can e.g. Contain 1 to 12, especially 1 to 8, preferably 1 to 4 carbon atoms, e.g. be the methyl, ethyl, propyl, butyl, 2-methyl-butyl, 3,3-dimethylbutyl, pentyl, hexyl or octyl radical. Preferably di, tri and tetra substituted olefins can be reacted e.g. Propene, but-1-ene, isobutene, pent-1-ene, hex-1-ene, but-2-ene, 2-methylbut-2-ene, 3-methylpent-2-ene, 3,5-dimethyln- 2-ene, tetramethylethylene.
Im allgemeinen können 1,5 bis 4, vorteilhaft 2 bis 3, insbesondere 2 bis 2,5 mol Olefin pro Mol Benzylhalogenid I verwendet werden. Niedrigere, z.B. äquimolare Olefinmengen sind möglich, aber nicht zweckmäßig, da der bei der Reaktion entstehende Halogenwasserstoff eventuell vom Olefin gebunden und dadurch verbraucht werden kann. Höhere Überschüsse an Olefin sind dagegen möglich, bringen aber in der Regel keine Vorteile.In general, 1.5 to 4, advantageously 2 to 3, in particular 2 to 2.5, moles of olefin can be used per mole of benzyl halide I. Lower, e.g. Equimolar amounts of olefins are possible, but not expedient, since the hydrogen halide formed in the reaction can possibly be bound by the olefin and thereby consumed. Higher excesses of olefin, on the other hand, are possible, but generally have no advantages.
Die Umsetzung wird erfindungsgemäß in Gegenwart katalytischer Mengen an Titantetrachlorid durchgeführt, da dieser Katalysator die Ringschlußreaktion zum Indan besonders begünstigt. Die Katalysatormenge liege zweckmäßigerweise bei 0,002 bis 0,2, insbesondere 0,004 bis 0,04, vorzugsweise 0,01 bis 0,03 mol, bezogen auf 1 mol Benzylhalogenid I. Bei geringeren und höheren Katalysatormengen nimmt im allgemeinen die Bildung von Nebenprodukten zu.According to the invention, the reaction is carried out in the presence of catalytic amounts of titanium tetrachloride, since this catalyst particularly favors the ring closure reaction to indane. The amount of catalyst is expediently from 0.002 to 0.2, in particular 0.004 to 0.04, preferably 0.01 to 0.03 mol, based on 1 mol of benzyl halide I. With smaller and higher amounts of catalyst, the formation of by-products generally increases.
Die Umsetzung kann in Gegenwart oder in Abwesenheit eines Lösungsmittels durchgeführt werden. Als Lösungsmittel können die für Friedel-CraftsSHY -Reaktionen üblichen Lösungsmittel wie aromatische oder aliphatische Kohlenwasserstoffe, Ether oder halogenierte Kohlenwasserstoffe, z.B. Benzol, Toluol, Hexan, Diethylether, Dichlormethan, Chloroform von Lösungsmitteln nicht nötig, was das erfindungsgemäße Verfahren besonders auszeichnet.The reaction can be carried out in the presence or absence of a solvent. Solvents which can be used are the solvents customary for Friedel-CraftsSHY reactions, such as aromatic or aliphatic hydrocarbons, ethers or halogenated hydrocarbons, e.g. Benzene, toluene, hexane, diethyl ether, dichloromethane, chloroform of solvents are not necessary, which is particularly characteristic of the process according to the invention.
Die Reaktionstemperatur richtet sich nach der Reaktivität der Einsatzstoffe. Sie liegt in der Regel bei ca. -20 bis +40°C. Tiefere Temperaturen sind möglich, aber im allgemeinen nicht nötig. Die Durchführung kann in an sich bekannter Weise bei Überdruck, Unterdruck oder vorteilhaft bei Atmosphärendruck, diskontinuierlich oder kontinuierlich nach den dafür üblichen Techniken vorgenommen werden.The reaction temperature depends on the reactivity of the starting materials. It is usually around -20 to + 40 ° C. Lower temperatures are possible, but generally not necessary. The procedure can be carried out in a manner known per se at positive pressure, negative pressure or advantageously at atmospheric pressure, discontinuously or continuously using the techniques customary for this.
Beispielsweise kann man das Olefin bei der Reaktionstemperatur zusammen mit Titantetrachlorid vorlegen und das Benzylhalogenid I hinzufügen. Das erhaltene Umsetzungsgemisch wird in an sich üblicher Weise aufgearbeitet, indem man z.B. den Katalysator durch Zugabe von Wasser zerstört, überschüssiges Olefin und flüchtige Nebenprodukte abdestilliert und das im Rückstand enthaltene Indan z.B. durch Destillation oder Umkristallisieren reinigt oder direkt weiterverwendet.For example, the olefin can be introduced at the reaction temperature together with titanium tetrachloride and the benzyl halide I added. The reaction mixture obtained is worked up in a conventional manner, e.g. the catalyst is destroyed by adding water, excess olefin and volatile by-products are distilled off and the indane contained in the residue is e.g. purified by distillation or recrystallization or used directly.
Nach dem erfindungsgemäßen Verfahren können gegebenenfalls substituierte Indane, insbesondere polyalkylsubstituierte Indane, auf technisch einfache Weise in guten Ausbeuten erhalten werden. Die Produkte, die als Zwischenprodukte z.B. für die Herstellung von Riechstoffen von Interesse sind, fallen häufig so rein an, daß sie direkt ohne destillative Reinigung weiterverarbeitet werden können. Die Herstellung von bicyclischen aromatischen Moschus-Riechstoffen wie Galaxolid aus den erfindungsgemäß erhaltenen Indanen ist z.B. in EP 89207 oder den US-Patenten 4 265 818 und 4 315 951 beschrieben.Optionally substituted indanes, in particular polyalkyl-substituted indanes, can be obtained in good yields in a technically simple manner by the process according to the invention. The products that are intermediates e.g. of interest for the production of fragrances are often so pure that they can be processed directly without purification by distillation. The production of bicyclic aromatic musk fragrances such as galaxolide from the indanes obtained according to the invention is e.g. in EP 89207 or U.S. Patents 4,265,818 and 4,315,951.
Bei -5°C wurden 1750 g (25 mol) 2-Methylbut-2-en zusammen mit 32 g (0,17 mol) Titantetrachlorid vorgelegt und innerhalb von 3 Stunden mit 1547 g (10 mol) 2-Chlor-2-phenylpropan (Cumylchlorid) versetzt, wobei die Temperatur nicht über +10°C anstieg. Anschließend wurde 1 h bei Raumtemperatur nachgerührt und das Reaktionsgemisch wie üblich aufgearbeitet, indem man 12,3 g (0,68 mol) Wasser zusetzte, bei Raumtemperatur rührte und nach Phasentrennung das überschüssige Olefin und das als Nebenprodukt entstandene tert.-Amylchlorid aus der organischen Phase abdestillierte.At -5 ° C., 1750 g (25 mol) of 2-methylbut-2-ene were introduced together with 32 g (0.17 mol) of titanium tetrachloride and within 3 hours with 1547 g (10 mol) of 2-chloro-2-phenylpropane (Cumyl chloride) were added, the temperature not rising above + 10 ° C. The mixture was then stirred at room temperature for 1 h and worked up as usual by adding 12.3 g (0.68 mol) of water, stirring at room temperature and after phase separation the excess olefin and the tert-amyl chloride formed as a by-product from the organic Phase distilled off.
Es verblieben 1851 g Rückstand, der gemäß gaschromatographischer Analyse 94 Gew.-% 1,1,2,3,3-Pentamethylindan, entsprechend einer Ausbeute von 92,5 %, bezogen auf Cumylchlorid, enthielt und direkt für Folgereaktionen weiterverwendet werden konnte.1851 g of residue remained which, according to gas chromatographic analysis, contained 94% by weight of 1,1,2,3,3-pentamethylindane, corresponding to a yield of 92.5%, based on cumyl chloride, and could be used directly for subsequent reactions.
Bei einer entsprechend Beispiel 1 jedoch in Gegenwart von 8 g (0,042 mol) Titantetrachlorid durchgeführten Umsetzung fiel das Produkt nach destillativer Reinigung in einer Ausbeute von 80,3 %, bezogen auf Cumylchlorid, an.In a reaction carried out in accordance with Example 1, but in the presence of 8 g (0.042 mol) of titanium tetrachloride, the product was obtained after purification by distillation in a yield of 80.3%, based on cumyl chloride.
a) 87,5 (1,25 mol) 2-Methylbut-2-en wurden zusammen mit 1,19 g (8,5 mmol) wasserfreiem Zinkchlorid in 0,38 g (5,1 mmol) Diethylether bei 0°C vorgelegt und bei dieser Temperatur innerhalb von 1 Stunde mit 78 g (0,5 mol) Cumylchlorid versetzt. Anschließend wurde 1 Stunde bei Raumtemperatur nachgerührt.a) 87.5 (1.25 mol) of 2-methylbut-2-ene together with 1.19 g (8.5 mmol) of anhydrous zinc chloride in 0.38 g (5.1 mmol) of diethyl ether were initially introduced at 0 ° C. and 78 g (0.5 mol) of cumyl chloride were added at this temperature within 1 hour. The mixture was then stirred at room temperature for 1 hour.
Nach üblicher Aufarbeitung und Abdestillieren von Leichtsiedern wurden 75,7 g Rückstand erhalten, der gemäß gaschromatographischer Analyse 11 Gew.-% 1,1,2,3,3-Pentamethylindan, entsprechend einer Ausbeute von 8,9 %, bezogen auf Cumylchlorid, enthielt.After the usual work-up and distillation of low boilers, 75.7 g of residue were obtained which, according to gas chromatographic analysis, contained 11% by weight of 1,1,2,3,3-pentamethylindane, corresponding to a yield of 8.9%, based on cumyl chloride .
b) Nach Umsetzung analog a), jedoch in Gegenwart von 132 ml Methylenchlorid, wurden 50,9 % 1,1,2,3,3-Pentamethylindan, bezogen auf Cumylchlorid, erhalten (gaschromatographisch ermittelt).b) After reaction analogous to a), but in the presence of 132 ml of methylene chloride, 50.9% of 1,1,2,3,3-pentamethylindane, based on cumyl chloride, were obtained (determined by gas chromatography).
110 g (1,31 mol) Tetramethylethylen und 82,8 g (0,535 mol) Cumylchlorid wurden in 1,6 1 Methylenchlorid gelöst und auf -75°C gekühlt. Innerhalb von 10 min wurden 10 ml Titantetrachlorid zugegeben und das Reaktionsgemisch 1 h bei -75°C gerührt. Die Lösung wurde anschließend auf 900 ml verdünnte Salzsäure gegossen, die organische Phase abgetrennt und getrocknet. Nach Abfiltrieren des Trockenmittels wurde der Rückstand nach Abtrennen von Leichtsiedern destilliert.
Ausbeute: 78,2 g (
Yield: 78.2 g (
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19863626227 DE3626227A1 (en) | 1986-08-02 | 1986-08-02 | METHOD FOR PRODUCING INDANES |
| DE3626227 | 1986-08-02 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0255650A2 true EP0255650A2 (en) | 1988-02-10 |
| EP0255650A3 EP0255650A3 (en) | 1988-10-05 |
| EP0255650B1 EP0255650B1 (en) | 1991-04-10 |
Family
ID=6306574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87110537A Expired - Lifetime EP0255650B1 (en) | 1986-08-02 | 1987-07-21 | Method for the production of indanes |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4740646A (en) |
| EP (1) | EP0255650B1 (en) |
| DE (2) | DE3626227A1 (en) |
| IL (1) | IL83272A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2065468T3 (en) * | 1989-04-14 | 1995-02-16 | Quest Int | PROCEDURE FOR THE PREPARATION OF RETHAL-SUBSTITUTED TETRALINES AND INDANOS. |
| US5068484A (en) * | 1989-11-02 | 1991-11-26 | Uop | Process for the hydroconversion of a feedstock comprising organic compounds having a tendency to readily form polymer compounds |
| DE19634684C1 (en) * | 1996-08-28 | 1998-03-12 | Basf Ag | Process for the preparation of indene derivatives |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3278621A (en) * | 1963-03-21 | 1966-10-11 | Polak Frutal Works | Process for preparing polyalkyltetralins |
| NL123427C (en) * | 1963-06-10 | |||
| US3272883A (en) * | 1963-12-27 | 1966-09-13 | Monsanto Co | Synthesis of 3-phenylindene |
| US4677238A (en) * | 1986-09-12 | 1987-06-30 | The Standard Oil Company | Preparation of indenes |
-
1986
- 1986-08-02 DE DE19863626227 patent/DE3626227A1/en not_active Withdrawn
-
1987
- 1987-07-21 EP EP87110537A patent/EP0255650B1/en not_active Expired - Lifetime
- 1987-07-21 DE DE8787110537T patent/DE3769238D1/en not_active Expired - Lifetime
- 1987-07-21 IL IL83272A patent/IL83272A/en not_active IP Right Cessation
- 1987-07-23 US US07/076,592 patent/US4740646A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| JOURNAL OF CHEMICAL RESEARCH (S), 1979, Seiten 184,185, Paris, FR; F. MARCUZZI et al.: "Synthesis and configuration of 1,2,3-triphenyl- and 1,3-diphenyl-2-methyl-indanes" * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3769238D1 (en) | 1991-05-16 |
| EP0255650B1 (en) | 1991-04-10 |
| US4740646A (en) | 1988-04-26 |
| IL83272A0 (en) | 1987-12-31 |
| DE3626227A1 (en) | 1988-02-04 |
| EP0255650A3 (en) | 1988-10-05 |
| IL83272A (en) | 1991-03-10 |
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